Patent GB-733808-A (GB)
Title: Oxidation of chemical compounds
IPC: C07J75/00
Filed: 1952-12-19
Abstract: Carbonyl compounds are prepared by reacting a primary or secondary alcohol with a tertiary organic base-chromium trioxide complex.  The reaction may be carried out in the presence of an inert non-acidic solvent, e.g., benzene, toluene, pyridine or picoline.  The primary or secondary alcohol may be an aliphatic alcohol or a phenanthrene or cyclopentanopolyhydrophenanthrene compound.  Suitable tertiary organic bases from which the complex may be prepared are pyridine, g -picoline, b -picoline, lutidines, quinoline, diethylformamide and triethylamine.  The complex may be formed in situ by dissolving the compound to be oxidized in a tertiary organic base and adding chromium trioxide.  Aldehydes are obtained from primary alcohols and ketones are obtained from secondary alcohols by using the above process.  The process is particularly useful for steroid compounds having a polyhydroxylated side chain at the 17-position to form the corresponding compound having a ketol side chain, for unsaturated steroid alcohols to form unsaturated steroid ketones without effecting the unsaturated linkage, and for unsaturated hydroxyphenanthrene compounds to form the corresponding keto-phenanthrene compounds without affecting the unsaturated nucleus.  In the examples 3-acetoxy-11,20-diketo pregnane is prepared from 3-acetoxy-11-keto-20-hydroxypregnane, 3,21 - diacetoxy - 17 - hydroxy - 11,20 - diketo - pregnane is prepared from 3,21 - diacetoxy - 11 - keto - 17,20 - dihydroxy - pregnane, D 8(a),22 - 3 - acetoxy - 7,11 - diketo - ergostadiene is prepared from D 8(a),22 - 3 - acetoxy - 7,11 - dihydroxy - ergostadiene, n - butyraldehyde is prepared from n-butyl alcohol, 4b-methyl - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7, 8,10,10a - dodecahydrophenanthrene - 1,4 - dione, 4b - methyl - 7 - ethylenedioxy - 1,2,3,4,4a, 4b,5,6,7,8,10,10a - dodecahydrophenanthrene - 1-one-4-ol and 4b-methyl-7-ethylenedioxy-1,2, 3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene-1-ol-4-one are prepared from 4b-methyl-7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydrophenanthrene-1,4-diol, 4b-methyl-7 - ethylene - dioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydrophenanthrene - 1 - ol - 4 - one - 1 - acetate is prepared from 4b-methyl-7-ethylenedioxy - 1,2,3,4,4a,5,6,7,8,10,10a p  - dodecahydrophenanthrene - 1,4 - diol - 1 - acetate, and 4b - methyl - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8, 10,10a - dodecahydrophenanthrene - 1,4 - dione is prepared from 4b-methyl-7-ethylenedioxy-1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene - 1 - one - 4 - ol and from 4b - methyl - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydrophenanthrene - 1 - ol - 4 - one, all these oxidations being carried out with pyridine chromium trioxide complex, cortisone acetate is prepared by oxidizing hydrocortisone acetate with quinoline chromium trioxide complex, and 4b - methyl - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5, 6,7,8,10,10a - dodecahydrophenanthrene - 1,4 - dione is prepared by oxidizing 4b-methyl-7-ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene - 1 - ol - 4 - one with triethylamine chromium trioxide complex.  Organic tertiary base chromium trioxide complexes are prepared by the direct reaction of the base and chromium trioxide.  Organic tertiary bases referred to are pyridine, g - and b -picoline, lutidines, quinoline, triethylamine and diethylformamide.